EP4180120A1 - Catalyseur de purification de gaz d'échappement - Google Patents
Catalyseur de purification de gaz d'échappement Download PDFInfo
- Publication number
- EP4180120A1 EP4180120A1 EP21854380.9A EP21854380A EP4180120A1 EP 4180120 A1 EP4180120 A1 EP 4180120A1 EP 21854380 A EP21854380 A EP 21854380A EP 4180120 A1 EP4180120 A1 EP 4180120A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- exhaust gas
- catalyst
- base material
- barium
- gas purification
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000003054 catalyst Substances 0.000 title claims abstract description 198
- 238000000746 purification Methods 0.000 title claims abstract description 86
- 239000000463 material Substances 0.000 claims abstract description 112
- 239000007789 gas Substances 0.000 claims abstract description 92
- 229910052788 barium Inorganic materials 0.000 claims abstract description 64
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000002245 particle Substances 0.000 claims abstract description 55
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 37
- 239000001301 oxygen Substances 0.000 claims abstract description 37
- 239000002131 composite material Substances 0.000 claims abstract description 32
- 239000011232 storage material Substances 0.000 claims abstract description 12
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 10
- 150000001553 barium compounds Chemical class 0.000 claims abstract description 5
- SBEQWOXEGHQIMW-UHFFFAOYSA-N silicon Chemical compound [Si].[Si] SBEQWOXEGHQIMW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims description 21
- 239000002184 metal Substances 0.000 claims description 21
- 238000003860 storage Methods 0.000 abstract description 22
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 44
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 20
- 239000002002 slurry Substances 0.000 description 13
- 239000010948 rhodium Substances 0.000 description 11
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000004215 Carbon black (E152) Substances 0.000 description 7
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 7
- 230000006866 deterioration Effects 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 150000002430 hydrocarbons Chemical class 0.000 description 7
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 229910000420 cerium oxide Inorganic materials 0.000 description 5
- 239000010419 fine particle Substances 0.000 description 5
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 4
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229910052878 cordierite Inorganic materials 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 3
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 3
- 238000005192 partition Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 231100000572 poisoning Toxicity 0.000 description 3
- 230000000607 poisoning effect Effects 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000005485 electric heating Methods 0.000 description 2
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- -1 Pr2O3 Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
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- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
- F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
- F01N3/24—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
- F01N3/28—Construction of catalytic reactors
- F01N3/2803—Construction of catalytic reactors characterised by structure, by material or by manufacturing of catalyst support
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- F01N3/2828—Ceramic multi-channel monoliths, e.g. honeycombs
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- B01D2255/20—Metals or compounds thereof
- B01D2255/209—Other metals
- B01D2255/2092—Aluminium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/40—Mixed oxides
- B01D2255/407—Zr-Ce mixed oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/90—Physical characteristics of catalysts
- B01D2255/902—Multilayered catalyst
- B01D2255/9022—Two layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/90—Physical characteristics of catalysts
- B01D2255/908—O2-storage component incorporated in the catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/90—Physical characteristics of catalysts
- B01D2255/92—Dimensions
- B01D2255/9202—Linear dimensions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/702—Hydrocarbons
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/01—Engine exhaust gases
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N2330/00—Structure of catalyst support or particle filter
- F01N2330/06—Ceramic, e.g. monoliths
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N2330/00—Structure of catalyst support or particle filter
- F01N2330/18—Composite material
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N2370/00—Selection of materials for exhaust purification
- F01N2370/02—Selection of materials for exhaust purification used in catalytic reactors
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N2510/00—Surface coverings
- F01N2510/06—Surface coverings for exhaust purification, e.g. catalytic reaction
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Definitions
- the present invention relates to an exhaust gas purification catalyst, and particularly to an exhaust gas purification catalyst preferably applicable as an electrically heated catalyst.
- An electrically heated catalyst has attracted attention as a catalyst for purifying an exhaust gas emitted from an engine of, for example, an automobile.
- the temperature of the exhaust gas purification catalyst needs to increase to a temperature at which the catalyst is activated.
- a typical exhaust gas purification catalyst is heated by using heat of an exhaust gas, and thus, if the temperature of the exhaust gas is low, for example, immediately after the engine has started, high purification performance cannot be obtained.
- the catalyst can be activated by increasing the temperature of the catalyst in a short time by energization heating. Thus, even if the temperature of the exhaust gas is low, sufficient purification performance can be obtained, and purification efficiency of the exhaust gas can be enhanced accordingly.
- a typical configuration of an electrically heated catalyst includes a base material and a catalyst layer.
- a known base material of an electrically heated catalyst contains silicon carbide (SiC), which is ceramic having conductivity.
- SiC silicon carbide
- a known example of this base material includes a silicon-silicon carbide (Si-SiC) composite material in which Si is bonded to SiC as a material having a lower resistance than SiC (see, for example, Patent Documents 1 and 2).
- a known catalyst layer of an electrically heated catalyst contains, for example, a platinum-group metal (PGM) as a catalyst component, and an oxygen storage material (OSC material) (see, for example, Patent Document 3).
- PGM platinum-group metal
- OSC material oxygen storage material
- an exhaust gas purification catalyst using a base material including a Si-SiC composite material when the catalyst is exposed to a high temperature, Si in the Si-SiC composite material migrates to a catalyst layer and is diffused therein to react with an oxygen storage material, resulting in the possibility of deterioration of the oxygen storage material.
- the catalyst layer contains a barium (Ba) component in order to suppress poisoning of a platinum-group metal by hydrocarbon (HC)
- the Ba element promotes diffusion of Si into the catalyst layer, and consequently, promotes deterioration of the oxygen storage material.
- the case where the barium component is contained in the catalyst layer of the exhaust gas purification catalyst using the base material including the Si-SiC composite material involves the problem of low deterioration resistance of oxygen storage capacity when exposed to high temperatures (i.e., durability of oxygen storage capacity to high temperatures).
- An exhaust gas purification catalyst disclosed here includes: a base material; and a catalyst layer in contact with the base material.
- the base material contains a silicon-silicon carbide composite material.
- the catalyst layer includes a platinum-group catalyst, a barium component, and an oxygen storage material.
- the barium component is at least one material selected from the group consisting of barium and a barium compound.
- the barium component is present at least on the surface of an oxygen storage material.
- the barium component has an average particle size of 100 nm or more and 350 nm or less.
- this configuration provides an exhaust gas purification catalyst that includes a base material containing a Si-SiC composite material and a catalyst layer containing a barium component and that has excellent high-temperature durability of oxygen storage capacity.
- the average particle size of the barium component is 100 nm or more and 200 nm or less. This configuration can further enhance high-temperature durability of the oxygen storage capacity.
- the platinum-group metal is Pd. This configuration can further enhance high-temperature durability of the oxygen storage capacity.
- the exhaust gas purification catalyst further includes an electrode, and the exhaust gas purification catalyst is an electrically heated catalyst.
- This configuration provides the electrically heated catalyst having excellent high-temperature durability of oxygen storage capacity.
- FIG. 1 schematically illustrates an example of an exhaust gas purification catalyst according to this embodiment.
- FIG. 1 is an example of a case where the exhaust gas purification catalyst according to this embodiment is configured as an electrically heated catalyst.
- FIG. 2 schematically illustrates a layered structure of the exhaust gas purification catalyst illustrated in FIG. 1 .
- an exhaust gas purification catalyst 10 includes a base material 11 and a catalyst layer 20.
- the catalyst layer 20 is disposed directly on the base material 11, and therefore, the catalyst layer 20 is in contact with the base material 11.
- the base material 11 is a member supporting the catalyst layer 20.
- the base material 11 contains a Si-SiC composite material. Since the base material 11 contains the Si-SiC composite material, high conductivity can be obtained. In addition, the Si-SiC composite material can function as a resistance heating body, and thus, the Si-SiC composite material contained in the base material 11 enables the exhaust gas purification catalyst 10 to be used as an electrically heated catalyst.
- the base material 11 may contain a component other than the Si-SiC composite material within the range that does not significantly inhibit advantages of the present invention.
- a ratio of Si to SiC (Si/SiC) in the Si-SiC composite material is not specifically limited, and may be the same as or similar to a ratio (Si/SiC) in a known Si-SiC composite material for use in a base material of an exhaust gas purification catalyst.
- the base material 11 may have a S or similar to that of a known exhaust gas purification catalyst.
- the base material 11 may be a straight-flow or wall-flow honeycomb base material that is generally used in an exhaust gas purification catalyst.
- the base material 11 has a cylindrical outer shape.
- the outer shape of the base material 11 is not limited to this example, and may be an oval cylindrical shape or a polygonal cylindrical shape, for example.
- Dimensions of the base material 11 are not specifically limited, and may be the same as or similar to those of a known exhaust gas purification catalyst used as an electrically heated catalyst.
- the base material 11 includes a plurality of cells 15 whose both ends at an exhaust gas inflow side and an exhaust gas outflow side are open, and partitions 16 partitioning adjacent ones of the cells 15.
- the shape of each cell 15 is not specifically limited, and may be a quadrangle such as a square, a parallelogram, a rectangle, or a trapezoid; another polygonal shape such as a triangle, a hexagon, or an octagon; or a circle, for example.
- an exhaust gas that has flowed into the cells 15 from the end at the exhaust gas inflow side passes through the cells 15 and flows out from the end at the exhaust gas outflow side.
- a catalyst layer 20 is formed in at least a portion of the base material 11. Although not shown in FIG. 1 , the catalyst layer 20 is formed in the cells 15.
- the catalyst layer 20 contains a platinum-group metal as a catalyst component.
- the catalyst layer 20 contains at least one metal selected from the group consisting of platinum (Pt), rhodium (Rh), palladium (Pd), ruthenium (Ru), osmium (Os), and iridium (Ir).
- Pd and Pt have high purification performance (performance in oxidation purification) of carbon monoxide (CO) and hydrocarbon (HC), and Rh has high purification performance (performance in reduction purification) of NOx.
- the platinum-group metal contained in the catalyst layer 20 is preferably at least one metal selected from the group consisting of Pt, Rh, and Pd.
- Si which causes degradation of oxygen storage capacity, is more easily diffused in the catalyst layer.
- Pd is more preferable as the platinum-group metal.
- the platinum-group metal is preferably fine particles.
- the platinum-group metal has an average particle diameter of preferably 15 nm or less, more preferably 10 nm or less, further preferably 7 nm or less, and most preferably 5 nm or less.
- the average particle diameter of the platinum-group metal is preferably 1 nm or more. It should be noted that the average particle diameter of the platinum-group metal can be determined by acquiring an electron microscopic image (e.g., TEM image) of the platinum-group metal and calculating an average value of particle diameters of 20 or more particles selected randomly in the image.
- the catalyst layer contains an oxygen storage material (so-called "OSC material”).
- the OSC material can function as a promoter of exhaust gas purification.
- the OSC material a compound known to have oxygen storage capacity may be used, and examples of the known compoud include ceria (CeO 2 ) and a composite oxide including ceria.
- the composite oxide including ceria include composite oxide (ceria-zirconia composite oxide, i.e., a CZ composite oxide or ZC composite oxide) including ceria and zirconia (ZrO 2 ).
- the OSC material contains zirconium oxide, thermal degradation of cerium oxide can be suppressed.
- the OSC material is preferably ceria-zirconia composite oxide.
- the OSC material may contain an oxide of a rare-earth element in order to enhance properties (especially heat resistance and oxygen storage/release property, for example).
- a rare-earth element examples include Sc, Y, La, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu.
- the content of cerium oxide is preferably 15 mass% or more, and more preferably 20 mass% or more.
- the content of cerium oxide is preferably 40 mass% or less, and more preferably 30 mass% or less.
- the OSC material can also function as a carrier of a catalyst, and the like.
- the platinum-group catalyst is typically supported by the OSC material.
- the catalyst layer 20 may further contain, as a carrier, an oxide (preferably alumina) other than the OSC material, such as alumina (Al 2 O 3 ), titania (TiO 2 ), zirconia (ZrO 2 ), or silica (SiO 2 ).
- the platinum-group catalyst may be supported by this oxide carrier or may be supported by both the OSC material and this oxide carrier.
- the oxide carrier other than the OSC material may be supplemented with a small amount (e.g., 1 mass% or more and 10 mass% or less) of an oxide of a rare-earth element such as Pr 2 O 3 , Nd 2 O 3 , La 2 O 3 , or Y 2 O 3 .
- a small amount e.g., 1 mass% or more and 10 mass% or less
- an oxide of a rare-earth element such as Pr 2 O 3 , Nd 2 O 3 , La 2 O 3 , or Y 2 O 3 .
- the catalyst layer 20 contains a barium component. Since the catalyst layer 20 contains the barium component, poisoning of the platinum-group metal by hydrocarbon (HC) can be suppressed. In a case where the platinum-group metal is Pd, the barium component can suppress sintering of Pd.
- HC hydrocarbon
- the barium component is at least one selected from the group consisting of barium and a barium compound.
- the barium compound include barium sulfate, barium acetate, barium nitrate, and barium carbonate. Among these compounds, barium sulfate and barium acetate are preferable, and barium sulfate is more preferable.
- the average particle size of the barium component is preferably as small as possible.
- the barium component has an average particle size of several nanometers (especially about 5 nm), the barium component has significantly high dispersibility.
- the barium component has an average particle size of 100 nm or more and 350 nm or less.
- the average particle size of the barium component By allowing the average particle size of the barium component to be significantly larger than about 5 nm, contact between a Ba element included in the catalyst layer 20 and Si included in the base material 11 can be reduced, and by allowing the average particle size of the Ba element to be in the range from 100 nm to 350 nm (both inclusive), the Ba element exists in a dispersed state in the catalyst layer 20 together with the platinum-group catalyst.
- the average particle size of the barium component within this range, diffusion of Si into the catalyst layer 20 can be suppressed by the Ba element.
- the average particle size of the barium component is preferably 100 nm or more and 200 nm or less, and more preferably 150 nm or more and 200 nm or less.
- Si-SiC base material 11 is less likely to be damaged, and high NOx purification performance can also be obtained.
- the average particle size of the barium component can be, for example, determined as follows. First, a portion of the catalyst layer 20 is collected as a sample from the exhaust gas purification catalyst 10. Next, an electron microscopic image of this sample is acquired using an electron microscope (e.g., scanning electron microscope (SEM) or transmission electron microscope (TEM)). Then, 20 or more particles each of which is entirely seen are selected from particles of the barium component appearing in the electron microscopic image, and the area of each selected particle is obtained. Diameters of circles each having an area equal to the area of each selected particle are calculated, and an arithmetic mean of these diameters is obtained. This arithmetic mean is defined as an average particle size.
- SEM scanning electron microscope
- TEM transmission electron microscope
- the average particle size of the barium component can be adjusted in a method for producing a catalyst layer using slurry containing a barium source, by controlling an average particle size of the barium source, for example.
- the barium component is present at least on the surface of the OSC material.
- the barium component is typically supported by the OSC material.
- the catalyst layer 20 may further contain the above-described oxide carrier other than the OSC material, and the barium component may be supported by both the OSC material and this oxide carrier. In this case, 10 mass% or more, 30 mass% or more, or 50 mass% or more of the barium component is supported by the OSC material, for example.
- a dispersion state of the barium component in the catalyst layer 20 is not specifically limited.
- the catalyst layer 20 is formed using a slurry in which a platinum-group catalyst source, a barium source, an OSC material, and an optional oxide carrier are mixed, barium component is uniformly dispersed in the catalyst layer 20.
- the content of the barium component in the catalyst layer 20 is not specifically limited.
- a ratio of the mass of the barium component converted in terms of sulfate to the mass of the platinum-group element is 1/80 or more and 20 or less.
- the catalyst layer 20 may further contain components (e.g., a binder and/or an additive) not described above.
- a binder include alumina sol and silica sol.
- the additive include a NO x adsorbent and a stabilizer.
- the content of the platinum-group metal in the catalyst layer 20 is not specifically limited.
- the content of the platinum-group metal in the catalyst layer 20 is 0.01 mass% or more and 8 mass% or less or 0.1 mass% or more and 5 mass% or less with respect to the total mass of the OSC material and the oxide carrier other than the OSC material, included in the catalyst layer 20.
- the thickness of the catalyst layer 20 may be 1 pm or more and 500 pm or less or may be 5 pm or more and 200 pm or less.
- the catalyst layer 20 may be formed only on a portion of the surface of the base material 11.
- the catalyst layer 20 may be formed only on a front portion of the base material 11 (e.g., only on a region up to 30% from the end of the base material 11 at the exhaust gas inflow side in the flow direction of an exhaust gas) or only on a rear portion of the base material 11 (e.g., only on a region up to 30% from the end of the base material 11 at the exhaust gas outflow side in the flow direction of the exhaust gas).
- the catalyst layer 20 may have a uniform composition in the entire layer, or may have different compositions within the range of this embodiment.
- the front portion and the rear portion of the base material 11 may contain different platinum-group catalysts.
- the exhaust gas purification catalyst 10 may include an element other than the base material 11 and the catalyst layer 20.
- the exhaust gas purification catalyst 10 is configured as an electrically heated catalyst.
- the exhaust gas purification catalyst 10 further includes an electrode 40 in addition to the base material 11 and the catalyst layer 20.
- the electrode 40 may be the same as or similar to an electrode included in a known electrically heated catalyst, and the electrode 40 may be a metal electrode or a carbon electrode, for example.
- the electrode 40 includes an electrode layer 42 disposed on the outer surface of the base material 11 and an electrode terminal 44.
- the electrode layer 42 has the function of diffusing a current.
- the configuration of the electrode 40 is not limited to this example as long as the base material 11 can be electrified.
- FIG. 3 illustrates another example of the exhaust gas purification catalyst according to this embodiment.
- An exhaust gas purification catalyst 10' illustrated in FIG. 3 further includes a second catalyst layer 30 in addition to the first catalyst layer 20.
- the first catalyst layer 20 has a structure same as the structure described above.
- the second catalyst layer 30 includes a catalyst.
- the type of the catalyst included in the second catalyst layer 30 is not specifically limited.
- the second catalyst layer 30 may contain an oxide carrier, an OSC material for supporting a catalyst, and the like.
- the second catalyst layer 30 may contain Ba or may not contain Ba.
- the average particle size of the Ba particles is not specifically limited, and may be less than 100 nm, may exceed 350 nm, or may be within the range from 100 nm or more and 350 nm or less.
- the first catalyst layer 20 contains Pd, an oxide carrier (e.g., alumina) supporting Pd, Ba having an average particle size of 100 nm or more and 350 nm or less, and an OSC material (e.g., CZ composite material) supporting Ba.
- the second catalyst layer 30 contains Rh, an oxide carrier (e.g., alumina) supporting Rh, and an OSC material (e.g., CZ composite material).
- the exhaust gas purification catalyst 10 can be, for example, produced as follows. First, a base material 11 containing a Si-SiC composite material is prepared. Constituents of a catalyst layer 20, for example, a platinum-group metal source such as a solution containing ions of a platinum-group metal, an OSC material, a Ba source (e.g., barium sulfate or barium acetate), and a dispersion medium are mixed, thereby preparing slurry for forming the catalyst layer 20. This slurry is applied into cells 15 of the base material 11, is dried, and when necessary, is fired. Thereby, the catalyst layer 20 is formed on the base material 11. Thereafter, the electrode 40 is attached in accordance with a conventional method.
- a platinum-group metal source such as a solution containing ions of a platinum-group metal, an OSC material, a Ba source (e.g., barium sulfate or barium acetate), and a dispersion medium are mixed, thereby preparing s
- the exhaust gas purification catalyst 10 can be used for exhaust gas purification of an internal combustion engine according to a known method. Specifically, for example, the exhaust gas purification catalyst 10 is disposed and used in an exhaust system (especially an exhaust pipe) of an automobile engine. Here, the exhaust gas purification catalyst 10 is configured as an EHC. In this case, the exhaust gas purification catalyst 10 is electrically connected to an automobile such that electricity is supplied from, for example, a battery of the automobile.
- the internal combustion engine is, for example, a gasoline engine or a diesel engine, and is preferably a gasoline engine.
- the exhaust gas purification catalyst 10 has excellent high-temperature durability of oxygen storage capacity.
- the exhaust gas purification catalyst according to this embodiment is configured as an electrically heated catalyst
- the exhaust gas purification catalyst according to this embodiment may also be used as a fine particle collecting filter such as a gasoline particulate filter (GPF) or a diesel particulate filter (DPF).
- GPF gasoline particulate filter
- DPF diesel particulate filter
- a honeycomb base material of a Si-SiC composite material (volume: 551 mL, the number of cells: 600 cpsi, partition thickness: 5 mil, cell shape: quadrangle, and base material length: 50 mm) was prepared.
- a palladium nitrate solution, La 2 O 3 -modified Al 2 O 3 powder, CZ composite oxide powder supplemented with minute amounts of Pr 2 O 3 , Nd 2 O 3 , La 2 O 3 , and Y 2 O 3 , barium sulfate having an average particle size of 100 nm, a Al 2 O 3 -based binder, and ion-exchanged water were mixed, thereby preparing Pd-containing slurry.
- the Pd-containing slurry was poured into the base material, and an unnecessary portion of the slurry was blown out by a blower, thereby coating a wall surface of the base material with the slurry.
- the base material was placed in a drier at 120 °C and dried for two hours. Thereafter, the base material was fired at 500 °C for two hours in an electric heating furnace, thereby forming a Pd catalyst layer as a first catalyst layer.
- Rh-containing slurry A rhodium nitrate solution, La 2 O 3 -modified Al 2 O 3 powder, CZ composite oxide powder supplemented with minute amounts of Pr 2 O 3 , Nd 2 O 3 , La 2 O 3 , and Y 2 O 3 , an Al 2 O 3 -based binder, and ion-exchanged water were mixed, thereby preparing Rh-containing slurry.
- This Rh-containing slurry was poured onto the base material on which the Pd catalyst layer had been formed, and an unnecessary portion of the slurry was blown out by a blower, thereby coating a wall surface of the base material on which the Pd catalyst layer had been formed with the slurry.
- the base material was placed in a drier at 120 °C and dried for two hours. Thereafter, the base material was fired at 500 °C for two hours in an electric heating furnace, thereby forming a Rh catalyst layer, as a second catalyst layer, on the Pd catalyst layer.
- an exhaust gas purification catalyst according to Example 1 in which the Pd catalyst layer and the Rh catalyst layer were sequentially stacked on the base material was obtained.
- a supported amount of Pd was 2 g/L
- a supported amount of Rh was 0.15 g/L.
- Exhaust gas purification catalysts were produced in a manner similar to Example 1 except for using compounds having average particle sizes shown in the table below as barium components. It should be noted that an average particle size of barium sulfate having an average particle size of 50 nm or more was adjusted by wet grinding. For barium sulfate having an average particle size of 5 nm, water-soluble Ba was used for preparing slurry.
- a honeycomb base material of cordierite (volume: 551 mL, the number of cells: 600 cpsi, partition thickness: 4 mil, cell shape: quadrangle, and base material length: 50 mm) was prepared.
- Exhaust gas purification catalysts were produced in a manner similar to Example 1 except for using this cordierite base material and using compounds having average particle sizes shown in the table below as a barium component.
- the average particle size of barium acetate used was evaluated with a TEM, and the average particle size of barium sulfate used was evaluated with FE-SEM and laser diffraction particle size distribution analyzer.
- a portion of a catalyst layer of the exhaust gas purification catalyst produced above was taken as a sample, and an SEM image of the sample was acquired with a FE-SEM, and an average particle size was determined as an average value of particle sizes of 20 particles in the SEM image. Then, it was confirmed that the determined average particle size was equal to the average particle size of barium acetate used and barium sulfate used.
- An exhaust system of a V-type 8-cylinder gasoline engine placed on a base was equipped with exhaust gas purification catalysts of the examples, the comparative examples, and the reference examples and subjected to a durability test for 50 hours at a catalyst bed temperature of 1000°C under a condition including a predetermined fuel cut,
- An exhaust system of a gasoline engine placed on a base was equipped with the exhaust gas purification catalysts of the examples, the comparative examples, and the reference examples which had been subjected to the durability test described above.
- An O 2 sensor was disposed downstream of the catalysts.
- An air-fuel ratio A/F of a gas mixture to be supplied to the engine was switched repeatedly between rich and lean in a square-wave manner.
- a sum of an oxygen release amount and an oxygen absorption amount at this time was integrated, and an OSC was calculated.
- FIG. 4 shows results.
- the exhaust gas purification catalysts of the examples, the comparative examples, and the reference examples were disposed in an exhaust system of an engine bench, and a combustion state of the engine was controlled based on a stoichiometric air-fuel ratio.
- the temperature of an inflow gas into each catalyst was increased from 200 °C to 500 °C at a temperature rise speed of 10 °C/min. by using a heat exchanger.
- An intake air amount of the engine was 25 g/sec. Gas components of an inflow gas into the catalyst and an outflow gas from the catalyst during the temperature rise were analyzed, and a temperature at which 50% of a NOx component could be purified (50% purification temperature of NOx component: T50-NOx) was calculated.
- FIG. 5 shows results.
- the cordierite base material e.g., base material different from a Si-SiC base material
- the average particle size of the barium component decreased, high-temperature durability of oxygen storage capacity increased. This is because as the average particle size of the barium component decreases, the barium component is more highly dispersed, and the effect of suppressing poisoning of the platinum-group catalyst by HC is enhanced.
- the durability of oxygen storage capacity was high in the range where the average particle size of the barium component is 100 nm or more and 350 nm or less. This is because in the case of using the Si-SiC base material, by significantly increasing the average particle size of the barium component, contact between Ba included in the catalyst layer and Si included in the base material can be reduced, whereas by setting the average particle size within an appropriate range, the Ba element can be present in a dispersed state in the catalyst layer together with the platinum-group catalyst.
- the exhaust gas purification catalyst disclosed here has excellent high-temperature durability of oxygen storage capacity although the Si-SiC composite material is used in the base material and the barium component is used in the catalyst layer.
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JP2020134758A JP6986123B1 (ja) | 2020-08-07 | 2020-08-07 | 排ガス浄化用触媒 |
PCT/JP2021/027036 WO2022030241A1 (fr) | 2020-08-07 | 2021-07-19 | Catalyseur de purification de gaz d'échappement |
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EP4215274A4 (fr) * | 2020-09-18 | 2024-03-13 | Mitsui Mining & Smelting Co Ltd | Catalyseur chauffé électriquement pour la purification d'un gaz d'échappement |
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JPH1043598A (ja) * | 1996-08-02 | 1998-02-17 | Nissan Motor Co Ltd | 排気ガス浄化用触媒装置 |
JP4097749B2 (ja) * | 1997-10-03 | 2008-06-11 | 株式会社日本触媒 | 接触酸化用触媒 |
JP4296844B2 (ja) | 2003-05-28 | 2009-07-15 | スズキ株式会社 | 電気加熱式触媒装置 |
JP5261256B2 (ja) * | 2009-03-30 | 2013-08-14 | 日本碍子株式会社 | 通電発熱用ハニカム体及びその製造方法 |
JP5337876B2 (ja) * | 2009-05-27 | 2013-11-06 | 株式会社キャタラー | 排ガス浄化用触媒及びその製造方法 |
JP5599208B2 (ja) | 2010-03-19 | 2014-10-01 | 日本碍子株式会社 | ハニカム触媒体及び排ガス浄化装置 |
WO2013111457A1 (fr) * | 2012-01-23 | 2013-08-01 | エヌ・イーケムキャット株式会社 | Matériau à base d'alumine contenant du sulfate de baryum et catalyseur de purification de gaz d'échappement l'utilisant |
EP2826560A4 (fr) * | 2012-03-14 | 2015-12-09 | N E Chemcat Corp | Composition de catalyseur pour l'épuration des gaz d'échappement et catalyseur pour l'épuration des gaz d'échappement d'automobile |
JP6272303B2 (ja) * | 2013-03-28 | 2018-01-31 | エヌ・イーケムキャット株式会社 | 硫酸バリウムを含むアルミナ材料とその製造方法、それを用いた排気ガス浄化用触媒 |
JP6052250B2 (ja) | 2014-07-29 | 2016-12-27 | トヨタ自動車株式会社 | 通電加熱式触媒装置 |
JP6785901B2 (ja) | 2019-02-21 | 2020-11-18 | 株式会社フジクラ | フィルタ装置、レーザ装置 |
CN111468114B (zh) * | 2020-05-09 | 2022-12-09 | 昆明贵研催化剂有限责任公司 | 一种具备高热稳定性的柴油机氧化型催化剂及其制备方法 |
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- 2021-07-19 EP EP21854380.9A patent/EP4180120A4/fr active Pending
- 2021-07-19 WO PCT/JP2021/027036 patent/WO2022030241A1/fr unknown
- 2021-07-19 US US18/019,162 patent/US20230302434A1/en active Pending
- 2021-07-19 CN CN202180056716.1A patent/CN116133736A/zh active Pending
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Publication number | Priority date | Publication date | Assignee | Title |
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EP4215274A4 (fr) * | 2020-09-18 | 2024-03-13 | Mitsui Mining & Smelting Co Ltd | Catalyseur chauffé électriquement pour la purification d'un gaz d'échappement |
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CN116133736A (zh) | 2023-05-16 |
WO2022030241A1 (fr) | 2022-02-10 |
JP2022030628A (ja) | 2022-02-18 |
EP4180120A4 (fr) | 2023-11-22 |
JP6986123B1 (ja) | 2021-12-22 |
US20230302434A1 (en) | 2023-09-28 |
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